Polyaniline/Pt Hybrid Nanofibers: High-Efficiency Nanoelectrocatalysts for Electrochemical Devices

A simple and facile procedure to synthesize a novel hybrid nanoelectrocatalyst based on polyaniline (PANI) nanofiber-supported supra-high density Pt nanoparticles (NPs) or Pt/Pd hybrid NPs without prior PANI nanofiber functionalization at room temperature is demonstrated. This represents a new type of ID hybrid nanoelectrocatalyst with several important benefits. First, the procedure is very simple and can be performed at room temperature using commercially available reagents without the need for templates and surfactants. Second, ultra-high density small "bare" Pt NPs or Pt/Pd hybrid NPs are grown directly onto the surface of the PANI nanofiber, without using any additional linker. Most importantly, the present PANI nanofiber-supported supra-high density Pt NPs or Pt/Pd hybrid NPs can be used as a signal enhancement element for constructing electrochemical devices with high performance.

Evaluation of coverage of self-assembled polyaniline-analogue monolayer by capacitance measurements

A method is developed to estimate the coverage of an electropolymerizable aniline-analogue monolayer (mixture of 2- and 3-aminophenols, 2/3-ATP) by measuring the charge capacitance of the electrode (theta = 81%). The technique of filling the uncovered area (defect sites) of the aniline-analogue monolayer with alkanethiols with long alkane chains (1-decanethiol, 1-DT) has been used to determine the coverage. The dielectric constant (permittivity) of the PANI-analogue monolayer was determined to 8.4. Adsorption kinetics of 1-DT was also studied, and the value of the rate constant of the secondary adsorption was measured to 0.9 mol(-1) dm(3) s(-1).

Synthesis and characterization of electroactive and biodegradable ABA block copolymer of polylactide and aniline pentamer

A triblock copolymer PLA-b-AP-b-PLA (PAP) of polylactide (PLA) and aniline pentamer (AP) with the unique properties of being both electroactive and biodegradable is synthesized by coupling an electroactive carboxyl-capped AP with two biodegradable bihydroxyl-capped PLAs via a condensation reaction. Three different molecule weight PAP copolymers are prepared. The PAP copolymers exhibit excellent electroactivity similar to the AP and polyaniline, which may stimulate cell proliferation and differentiation. The electrical conductivity of the PAP2 copolymer film (similar to 5 x 10(-6) S/cm) is in the semiconducting region. Transmission electron microscopic results suggest that there is microphase separation of the two block segments in the copolymer, which might contribute to the observed conductivity. The biodegradation and biocompatibility experiments in vitro prove the copolymer is biodegradable and biocompatible. Moreover, these new block copolymer shows good solubility in common organic solvents, leading to the system with excellent processibility. These biodegradable PAP copolymers with electroactive function thus possess the properties that would be potentially used as scaffold materials for neuronal or cardiovascular tissue engineering.

Electroactive oligoaniline-containing self-assembled monolayers for tissue engineering applications

A novel electroactive silsesquioxane precursor, N-(4-aminophenyl)-M-(4'-(3-triethoxysilyl-propyl-ureido) phenyl-1,4-quinonenediimine) (ATQD), was successfully synthesized from the emeraldine form of amino-capped aniline trimers via a one-step coupling reaction and subsequent purification by column chromatography. The physicochemical properties of ATQD were characterized using mass spectrometry as well as by nuclear magnetic resonance and UV-vis spectroscopy. Analysis by cyclic voltammetry confirmed that the intrinsic electroactivity of ATQD was maintained upon protonic acid doping, exhibiting two distinct reversible oxidative states, similar to polyaniline. The aromatic amine terminals of self-assembled monolayers (SAMs) of ATQD on glass substrates were covalently modified with an adhesive oligopeptide, cyclic Arg-Gly-Asp (RGD) (ATQD-RGD). The mean height of the monolayer coating on the surfaces was similar to 3 nm, as measured by atomic force microscopy. The biocompatibility of the novel electroactive substrates was evaluated using PC12 pheochromocytoma cells, an established cell line of neural origin. The bioactive, derivatized electroactive scaffold material, ATQD-RGD, supported PC12 cell adhesion and proliferation, similar to control tissue-culture-treated polystyrene surfaces.

Loosely packed self-assembled monolayer of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole on gold and its application in biomimetic membrane research

Dithiols of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole (HDMC) have been synthesized and employed to form self-assembled monolayers (SAMs) on gold. One characteristic of the HDMC molecule is its peculiar molecular structure consisting of a large and rigid headgroup and a small and flexible alkyl-chain tail. HDMC adsorbates can attach to gold substrates by a strong Au-S bond with weak van der Waals interactions between the alkyl-chain tails, leading to a loosely packed hydrophobic SAM. In this way we can couple hybrid bilayer membranes (HBMs) to gold surfaces with more likeness to a cell bilayer than the conventional HBMs based on densely packed long-chain alkanethiol SAMs. The insulating properties and stability of the HDMC monolayer as well as the HDMC/lipid bilayer on gold have been investigated by electrochemical techniques including cyclic voltammetry and impedance spectroscopy. To test whether the quality of the bilayer is sufficiently high for biomimetic research, we incorporated the pore-forming protein a-hemolysin) and the horseradish peroxidase into the bilayers, respectively.

Immobilization of the nanoparticle monolayer onto self-assembled monolayers by combined sterically enhanced hydrophobic and electrophoretic forces

The immobilization of surface-derivatized gold nanoparticles onto methyl-terminated self-assembled monolayers (SAMs) on gold surface was achieved by the cooperation of hydrophobic and electrophoretic forces. Electrochemical and scanning probe microscopy techniques were utilized to explore the influence of the SAM's structure and properties of the nanoparticle/SAM/gold system. SAMs prepared from 1-decanethiol (DT) and 2-mercapto-3-n-octylthiophene (MOT) were used as hydrophobic substrates. The DT SAM is a closely packed and organized monolayer, which can effectively block the underlying gold and inhibit a variety of solution species including organic and inorganic molecules from penetrating, whereas the MOT monolayer is poorly packed or disorganized (because of a large difference in dimension between the thiophene head and the alkylchain tail) and permeable to many organic probes in aqueous solution but not to inorganic probes. Thus, the MOT monolayer provides a more energetically favorable hydrophobic surface for the penetration and adsorption of organic species than the DT monolayer.

Electrically conductive, melt-processed ternary blends of polyaniline/dodecylbenzene sulfonic acid, ethylene/vinyl acetate, and low-density polyethylene

Although polyaniline (PANI) has high conductivity and relatively good environmental and thermal stability and is easily synthesized, the intractability of this intrinsically conducting polymer with a melting procedure prevents extensive applications. This work was designed to process PANI with a melting blend method with current thermoplastic polymers. PANI in an emeraldine base form was plasticized and doped with dodecylbenzene sulfonic acid (DBSA) to prepare a conductive complex (PANI-DBSA). PANI-DBSA, low-density polyethylene (LDPE), and an ethylene/vinyl acetate copolymer (EVA) were blended in a twin-rotor mixer. The blending procedure was monitored, including the changes in the temperature, torque moment, and work. As expected, the conductivity of ternary PANI-DBSA/LDPE/EVA was higher by one order of magnitude than that of binary PANI-DBSA/LDPE, and this was attributed to the PANI-DBSA phase being preferentially located in the EVA phase. An investigation of the morphology of the polymer blends with high-resolution optical microscopy indicated that PANI-DBSA formed a conducting network at a high concentration of PANI-DBSA. The thermal and crystalline properties of the polymer blends were measured with differential scanning calorimetry. The mechanical properties were also measured.

Fabrication and characterization of ordered oligoaniline film

highly organized phenyl-capped teraniline (PC-teraniline) film at the molecular level was fabricated on carbon surfaces by electrochemical reduction of diazonium salts. Cyclic voltammetry (CV). scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were employed for the characterization of the film.

In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Characterization and properties of the neutral and doped blends of poly(3-dodecylthiophene) with low-density polyethylene

In this paper, the structures and properties of the neutral and doped blends of poly(3-dodecylthiophene) (P3DDT) with low-density polyethylene (LDPE) were investigated. Wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), Fourier transform infrared spectra (FTIR), and scanning electron microscopy (SEM) were used to characterize the structures and morphologies of the blends, and conductivity was also measured. It was found that separate crystallizations occur between P3DDT and LDPE. When the amount of P3DDT is small in the blend, it has the effect of a nucleation reagent and has some influence on the crystal structure. After doping, the interaction force between the molecular chains increases, and leads to a more compact packing and a more uniform dispersion in morphology. Through blending, the thermal stability of pure component could be greatly improved, especially when the P3DDT content is 5 wt %. The conductivity measurements indicate that the conductivity increases with the increase of the P3DDT composition and doping time.

Stimulated emission in the blue wavelength region from a copolymer containing PPV segment

The lasing properties of a soluble conjugated polymer, Poly[1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1,2-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene] (CNMBC-Ph) in chloroform solution were investigated. The third harmonic radiation of a Nd:YAG laser was used as the pump light. The stimulated emission with a linewidth of 15 nm was observed in the blue wavelength region with the peak at 450 nm. The threshold pulse peak power was about 2.8 MW/cm(2). The energy conversion yield of the laser was estimated to be about 3.4%. The maximum peak power of the laser output pulse reached 40 kW. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Morphology of conductive blend fibers of polyaniline and polyamide-11

Polyaniline (PANI), a member of the intrinsically conducting polymer (ICPs) family, was blended with polyamide-11 (polyco-aminoundecanoyle) in concentrated sulfuric acid. The above solution was used to spin conductive PANI/polyamide-11 fibers by wet-spinning technology. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were employed to study the two-phase morphology of the conductive PANI/polyamide-11 fibers. The micrographs of the cross-section, the axial section and the surface of the monofilament demonstrated that the two blend components were incompatible. The morphology of PANI in the fibers was of fibrillar form, which was valuable for producing conducting channels. The electrical conductivity of the fibers was from 10(-6) to 10(-1) S/cm with the different PANI fraction and the percolation threshold was about 5 wt.%. By comparing the two blend systems of PANI/Polyamide-11 fibers and carbon black filled poly(ethylene terephthalate) (PET) fibers, it was shown that the morphology of the conductive component had an influence on electrical conductivity, The former had higher conductivity and lower percolation threshold than the latter. (C) 2001 Elsevier Science B.V. All rights reserved.

Mixed ion transfer analysis in redox processes of electroactive thin films

Electrochemical quartz crystal microbalance (EQCM) technique was used to measure the ion transfer in redox processes in electroactive organic thin films, such as self-assembled monolayer (SAM) (4-pyridyl hydroquinone, abbr. 4PHQ), multilayer based on SAM and conducting polymer film (here poly-(3,4-ethylenedioxythiophene), abbr. PEDOT). A mechanism of mixed ion transfer is developed and presented. Analysis of mixed ion transfer during redox processes successfully elucidates the deviation of oscillation frequency of the quartz crystal from theoretical expectation.

Stimulated emission in blue wavelength region from a copolymer

A dye laser based on the soluble conjugated polymer, Poly[1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene-1, 4-phenylene-1,2-ethenylene-3,5-dimethoxy-1,4-phenylene], has been fabricated. The laser was pumped by light pulses from the third harmonic radiation of an Nd:YAG laser. The lasing was observed in the blue wavelength region with the peak at 450 nm. The threshold energy is about 19 mu J. The energy conversion yield of the laser is about 3.4%. The maximum peak power of the laser output pulse arrives at about 20 kW.

Direct electron communication between glucose oxidase and carbon electrode covered with polypyrrole

Glucose oxidase can be effectively adsorbed onto the polypyrrole(PPy) thin film electrochemically formed on an anodized galssy carbon electrode(GCEa). Direct electron communication between the redox of GOD and the modified electrode was successfully achieved, which was detected using cyclic voltammetry. GOD entrapped in PPy film still remained its biological activity and could catalyze the oxidation of glucose. As a third generation biosensor, GOD-PPy/GCEa responded linearly up to 20 mM glucose with a wider linear concentration range.